KR20150070224A - Bisphosphite mixture and use thereof as a catalyst mixture in hydroformylation - Google Patents

Abstract

The present invention relates to a bisphosphite mixture, to a process for its preparation and to its reaction with a metal to form a mixture containing a structural isomer bisphosphite and a complex compound of a metal, and to a catalytically active composition in a hydroformylation reaction As well as the corresponding hydroformylation reactions.

Description

BISPHOSPHITE MIXTURE AND USE THEREOF AS A CATALYST MIXTURE IN HYDROFORMYLATION < RTI ID = 0.0 >

The present invention relates to a mixture of bisphosphites, a process for its preparation, and its reaction with metals to produce mixtures comprising structural isomeric bisphosphites and complexes of metals, and to the catalytically active compositions in hydroformylation reactions , And also the hydroformylation reaction itself.

The reaction between an olefin compound, carbon monoxide and hydrogen in the presence of a catalyst to produce an aldehyde having one more carbon atom is known as the hydroformylation or oxo method. The catalyst used in this reaction is frequently a compound of the transition metal of Group VIII of the Periodic Table of the Elements. The known ligand is, for example, compounds from a phosphine, a phosphite and a phosphine of the nitro class PO having a trivalent phosphorus P ^III, respectively. A good overview of the statement of hydroformylation of olefins is given in [B. CORNILS, WA HERRMANN, "Applied Homogeneous Catalysis with Organometallic Compounds ", vol. 1 & 2, VCH, Weinheim, New York, 1996] or [R. Franke, D. Selent, A. Boerner, "Applied Hydroformylation ", Chem. Rev., 2012, DOI: 10.1021 / cr3001803].

All catalytically active compositions have their particular advantages. Thus, depending on the feedstock and the target product, different catalytically active compositions are used.

Patents US 4 699 109 and US 4 879 416 describe their use in the hydroformylation of olefins at low pressure and at low synthesis gas pressures. Especially in the case of the hydroformylation of propene, this type of ligand achieves high activity and high n / i selectivity (ratio of linear aldehyde (= n) to n / i = branched (= iso) aldehyde) . WO 95/30680 discloses its use in catalysis including bidentate phosphine ligands and hydroformylation reactions. For example, patent specifications US 4 169 861, US 4 201 714 and US 4 193 943 describe a ferrocene-bridged bisphosphine as a ligand for hydroformylation.

A disadvantage of bidentate and multidentate phosphine ligands is that they require a relatively high level of complexity for their preparation. Therefore, it is often impractical to use such a system in industrial work. An additional factor is the relatively low activity that must be supplemented by chemical engineering over a high residence time. Which in turn leads to undesired side reactions of the product.

The rhodium monophosphite complexes in the catalytically active composition are suitable for the hydroformylation of branched olefins having internal double bonds, but the selectivity for the compounds which are hydroformylated at the ends is low. EP 0 155 508 discloses the use of bisarylene-substituted monophosphites in rhodium-catalyzed hydroformylation of sterically hindered olefins, for example isobutene.

The catalytically active compositions based on rhodium-bisphosphite complexes are suitable for the hydroformylation of linear olefins having terminal and internal double bonds, which mainly form a terminal hydroformylation product. In contrast, branched olefins having internal double bonds are only converted to a lesser extent. When they are coordinated to the transition metal sites, these phosphites generate catalysts with enhanced activity, but the useful lifetime characteristics of such catalytically active compositions are unsatisfactory and one reason is that the hydrolysis sensitivity of the phosphite ligands to be. The use of substituted bisaryldiols as starting materials for phosphite ligands has achieved significant improvements as described in EP 0 214 622 or EP 0 472 071.

According to the literature, the catalytically active compositions of these ligands based on rhodium are particularly active in the hydroformylation of? -Olefins. Patents US 4 668 651, US 4 748 261 and US 4 748 261 describe polyphosphite ligands which are capable of converting an alpha-olefin, also 2-butene, into a terminal hydroformylation product with high n / i selectivity. This type of bidentate ligand was also used for the hydroformylation of butadiene (US 5 312 996).

The bisphosphite disclosed in EP 1 294 731 has an olefin conversion of up to 98% in the hydroformylation of n-octene mixtures. However, the n-selectivity for the desired neonald also requires an improvement from 36.8% to a maximum of 57.6%. It is furthermore true that the use of the catalytically active composition in industrial work requires an effective lifetime measured in days rather than hours.

The document discloses the synthesis of symmetrical bisphosphites as disclosed after US 4 769 498 and its use in catalytically active transition metal-containing compositions for the hydroformylation of unsaturated compounds.

The bisphosphite disclosed under the formula V in column 8 of US 5 288 918 is a symmetric bisphosphite. Bisphosphite is also symmetric even when X ¹ and X ² are different radicals as in the case of reference numerals 2 and 3 in the table of column 11.

In US 4 769 498, and also in US 5 723 641, preferably symmetrical bisphosphites are prepared and used as ligands for hydroformylation. The symmetrical bisphosphite ligands used in the hydroformylation are prepared at low temperatures. According to these US publications, compliance with such low temperatures is absolutely necessary since higher temperatures will result in rearrangement and ultimately unwanted asymmetric bisphosphite here.

When used as ligands in transition metal-catalyzed hydroformylation, such asymmetric bisphosphites have much lower reactivity and lower n-position selectivity; Rhodium-catalyzed Hydroformylation, ed. by P. W. N. M. van Leeuwen and C. Claver, Kluwer Academic Publishers 2006, AA Dordrecht, NL] 45-46.

As described by van Leeuwen, symmetric bisphosphites have higher selectivity as well as greater reactivity. In addition to the goals of high reactivity and n-selectivity with respect to the unsaturated compounds to be carbonylated, catalysts made of metals, ligands and further components with activating action in each case in connection with the bisphosphites used as ligands ≪ / RTI > the stability of the composition which is active as a < RTI ID = 0.0 > With regard to the olefin-containing mixture, this is particularly true in the hydroformylation of a mixture of linear olefins in particular.

On pages 25-26 of US 5364950 and also in US 5763677 and ["Catalyst Separation, Recovery and Recycling ", edited by DJ Cole-Hamilton, RP Tooze, 2006, NL] "Is described. This "toxic phosphite" is formed during the use of an aryl phosphite-modified rhodium complex during the hydroformylation reaction. Wherein during the ligand decomposition, the aryl group is exchanged with the alkyl group in the hydroformylation product.

In addition to the formation of unwanted "toxic phosphites ", phosphite ligands can also be degraded during the hydrolysis reaction by trace amounts of water formed in aldehyde condensation.

The result of this decomposition reaction of the ligand is that the concentration of the hydroformylation-active rhodium complex species decreases with time and is accompanied by a loss of reactivity.

It is well known that, in the continuous mode of hydroformylation, the ligand (s) and optionally further components must be supplemented during the period of the reaction, that is to say after the start of the reaction (DE 10 2008 002 187 A1 Reference).

It is a technical object of the present invention to provide novel ligands which do not have the above-described drawbacks from the prior art in the hydroformylation of unsaturated compounds, but instead have the following characteristics:

1.) High active, and

2.) High n-position selectivity for hydroformylation and

3.) High effective life.

The high shelf life is determined by the fact that the hydroformylation-active composition comprising the ligand, together with additional ingredients, is capable of decomposing such ligand to a hydroformylation-inhibiting component, such as "toxic phosphite & It has a low tendency.

This object is achieved by a mixture comprising the following compounds (Ia) and (IIa):

Mixtures comprising compounds (Ia) and (IIa):

<Formula Ia>

<Formula IIa>

In this formula,

R1 is selected from -Me, -tBu, -OMe;

R2 is selected from -Me, -tBu, -OMe;

R3 is selected from -Me, -tBu, -OMe;

R4 is selected from -Me, -tBu, -OMe;

only,

When R1 is the same as R3, R2 is not the same as R4,

When R2 is the same as R4, R1 is not the same as R3,

P can participate in an additional combination.

Provided that when R1 is the same as R3, R2 is not the same as R4,

When R2 is the same as R4, R1 is not the same as R3 and the same substitution of all the biphenols is excluded.

In the case of Ia, there is an asymmetric bisphosphite, while in IIa there is a symmetric bisphosphite. Thus, the mixture comprises one symmetry and one asymmetric bisphosphite.

Usually, in the prior art, maximum purity ligands are used in the hydroformylation reaction because in each case different isomers strongly adversely affect the overall performance of the system. In general, asymmetric isomers would have existed as subcomponents, since only symmetric ligands are used in the hydroformylation.

Rhodium-catalyzed Hydroformylation, ed. Table 2 on page 45-46 of P. W. N. M. van Leeuwen and C. Claver, Kluwer Academic Publishers 2006, AA Dordrecht, NL describes the results of hydroformylation on symmetrical bifepofos ligands and their asymmetric isomers. In this connection it is obvious that the symmetric bipphosp ligand (at reference ligand 5a) is characterized by a much higher n / i selectivity and higher activity than its asymmetric isomer (at reference ligand 7). In the hydroformylation reaction of propene, the symmetrical ligand has an n / i selectivity of 53 and a reaction rate of 402, while an asymmetric ligand has a n / i selectivity of only 1.2 and a reaction rate of 280. Then, when using a mixture of two ligands, this would have resulted in a much inferior yield and n / i selectivity. A much worse overall performance was also recorded for the isomeric mixtures of ligands (7) and (8). Then, when the isomeric mixture of the present invention is used in the hydroformylation, this is not the case and other isomers may be present as subcomponents in the isomeric mixture without adversely affecting the overall performance of the system.

Thus, this is particularly advantageous since no additional purification steps are required during ligand preparation to obtain isomers with 100% purity. This is particularly advantageous because all the additional purification steps in the preparation of the ligand are more costly. Generally, several solvents are used for such purification and several tablets, such as recrystallization, are required under certain circumstances, which results in product loss as expected. The result, then, is that the preparation of the ligand is much more costly, which then adversely affects the overall economic viability of the industrial scale operation. It is therefore particularly advantageous to eliminate costly purification steps and to be able to use the isomeric mixtures in an industrial scale hydroformylation operation.

In one embodiment, the content of compound (Ia) is in the range of 0.5 to 99.5 mass%, and the content of compound (IIa) is in the range of 0.5 to 99.5 mass%.

The sum of the two compounds (Ia) and (IIa) is 100% by mass.

In one embodiment, the mixture comprises the following compounds (Ib) and (IIb):

(Ib)

<Formula IIb>

Wherein M is selected from Fe, Ru, Os, Co, Rh, Ir, Ni, Pd,

M can participate in additional joins.

In one embodiment, the content of compound (Ib) is in the range of 0.5 to 99.5 mass% and the content of compound (IIb) is in the range of 0.5 to 99.5 mass%.

The sum of the two compounds (Ib) and (IIb) is 100% by mass.

In one embodiment, the mixture comprises the following compounds (Ic) and (IIc):

<Formula I>

<Formula IIc>

In the above formula, M is selected from Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and Pt.

In one embodiment, the content of the compound Ic is in the range of 0.5 to 99.5 mass%, and the content of the compound IIc is in the range of 0.5 to 99.5 mass%.

The sum of the two compounds Ic and IIc is 100% by mass.

In one embodiment, the mixture further comprises at least one compound (Ia) or (IIa) that is not bound to M.

In one embodiment, M is Rh.

In one embodiment, R1 is -Me and R3 is not-Me.

In one embodiment, R 2 is -Me and R 4 is not -Me.

In one embodiment, R 1 and R 2 are each -Me.

In one embodiment, Rl is-tBu and R3 is not-tBu.

In one embodiment, R 2 is -OMe and R 4 is not -OMe.

The various mixtures may either be derived directly from the synthesis (meaning that the two isomers (Ia) and (IIa) are produced during one and the same synthesis) or may be synthesized from the pure compounds of formula (Ia) and (IIa) after synthesis.

In a preferred embodiment, the compound has the following structures (1Ia) and (2IIa):

&Lt; EMI ID =

&Lt; Formula

In a further preferred embodiment, the compound has the following structures (3Ia) and (4IIa):

&Lt; EMI ID =

&Lt; Formula

As examples of the various R radicals, compounds (1Ia), (2IIa), (3Ia) and (4IIa) are summarized in Table 1 below.

The present invention includes the following subjects:

a) a mixture of bisphosphites of formula Ia and Ha;

b) its preparation method;

c) a metal mixture of the following formulas Ib and IIb, wherein M is a metal from the group 4 to 10 of the Periodic Table of the Elements (Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt) And structural isomers of formula (Ia) and (IIa) that are not bound to the metal M are present;

(Ib)

<Formula IIb>

Wherein M is selected from Fe, Ru, Os, Co, Rh, Ir, Ni, Pd,

M can participate in additional joins.

d) a structural isomer as referred to under a), a metal from Groups 4 to 10 of the Periodic Table of the Elements (Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt) A composition comprising at least one additional component selected from the group comprising bisphosphites and bases, organic amines, epoxides, ion exchangers, buffer systems;

e) hydroformylation of unsaturated compounds and mixtures thereof with a composition according to d), a mixture of gases consisting of carbon monoxide and hydrogen, unsaturated compounds and mixtures thereof under the reaction conditions necessary for hydroformylation, and mixtures thereof;

f) A multiphasic reaction mixture consisting of:

f1) at least one composition according to d);

f2) a gas mixture comprising carbon monoxide and hydrogen;

f3) one or more unsaturated compounds as a substrate;

f4) at least one hydroformylation product formed from a substrate.

Compositions comprising such mixtures, as well as mixtures, are also claimed.

- the mixture described above,

- additional components selected from bases, organic amines, epoxides, buffer solutions, ion exchangers

&Lt; / RTI &gt;

In a preferred embodiment, the additional component used is a sterically hindered secondary amine.

It is also possible to use mixtures comprising two or more hindered amines.

The composition comprises, in addition to the mixture, the mixtures described above comprising at least one amine having 2,2,6,6-tetramethylpiperidine units.

More specifically, in the process according to the invention, an amine, di-4- (2,2,6,6-tetramethylpiperidinyl) sebacate, preferably having the formula (11) is used.

&Lt; Formula 11 >

A particularly preferred metal in the composition of the present invention is rhodium.

In addition to the mixture, the method of preparation thereof is also claimed.

a) oxidative coupling according to Scheme A,

<Reaction Scheme A>

b) oxidative coupling according to Scheme B below,

<Reaction Scheme B>

c) a step of reacting the product from a) with PCl ₃ according to Scheme C below,

<Reaction formula C>

d) reacting the product from b) with the product from c) to give the mixture according to claim 1

&Lt; / RTI &gt;

A particular advantage of the present invention is that the use of a mixture of structurally isomeric bisphosphites in the present invention instead of pure compounds eliminates the need for an inconvenient and costly separation of structural bisphosphite compounds, (Ia) and (IIa), especially (1Ia) and (2IIa), as described above in the milling.

From the prior art, reduced reactivity and lower n / i selectivity are expected due to the presence of asymmetric bisphosphite (Ia), especially its derivative (Ic). As shown in the subsequent hydroformylation experiments, the bisphosphite compounds (1Ia) and (2Ia) have surprisingly high reactivity and n / i selectivity as well as a noticeably increased useful life compared to the bisphosphites known from the prior art.

In one embodiment, the method further comprises the following method steps:

e) reacting with M to produce (Ib) and (IIb), wherein M is selected from Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt.

The use of mixtures as catalysts in the hydroformylation reaction of unsaturated compounds and mixtures thereof is further claimed. As used herein, the term "as a catalyst" should be interpreted as being used as a ligand for a metal complex which subsequently catalyses the reaction.

This defined mixture of bisphosphites consisting of the compounds of formulas Ia and Ha can be charged, for example, immediately before the start of the hydroformylation reaction. As such, this procedure differs from the general reaction in the stability study in that the specified isomer is charged first and the additional compound is formed only during the reaction.

A further process for the hydroformylation of unsaturated compounds and mixtures thereof is further claimed.

i) compositions described above,

ii) a gas mixture comprising carbon monoxide and hydrogen

&Lt; / RTI &gt; and mixtures thereof.

The unsaturated compounds which are hydroformylated in the process according to the invention comprise a hydrocarbon mixture obtained in a petrochemical processing plant. Examples of these include those referred to as C ₄ fractions. A typical composition of the C ₄ fraction from which most polyunsaturated hydrocarbons have been removed and which can be used in the process according to the invention is listed in the following Table 1 (see DE 10 2008 002188).

Core Content:

- HCC ₄ : A typical C ₄ mixture obtained from the C ₄ fraction from a steam cracking plant (high severity) after hydrogenation of 1,3-butadiene without further adjustment of the catalyst.

HCC ₄ / SHP: HCC ₄ composition wherein the residue of 1,3-butadiene is further reduced in the selective hydrogenation process / SHP.

- Raff. I (raffinate I): A typical C ₄ mixture obtained from the C ₄ fraction from a steam cracking plant (high severity) after removal of 1,3-butadiene (for example by NMP extraction rectification).

- Raff. I / SHP: A further reduction of 1,3-butadiene residues in the selective hydrogenation process / SHP. I composition.

- CC ₄ : A typical composition of the C ₄ fraction obtained from a catalytic cracking plant.

- CC ₄ / SHP: A composition of the C ₄ fraction wherein the residue of 1,3-butadiene is further reduced in the selective hydrogenation process / SHP.

In one variation of the method, the unsaturated compound or mixture thereof is selected from:

A hydrocarbon mixture from a steam cracking plant;

- a catalytic cracking plant, for example a hydrocarbon mixture from an FCC cracking plant;

- Oligomerization operations on homogeneous and heterogeneous phases, for example OCTOL, DIMERSOL, Fischer-Tropsch, Polygas, CatPoly, Hydrocarbon mixtures from InAlk, Polynaphtha, Selectopol, MOGD, COD, EMOGAS, NExOCTANE or SHOP processes;

A hydrocarbon mixture comprising a polyunsaturated compound;

- unsaturated carboxylic acid derivatives.

In one variation of the method, the mixture comprises an unsaturated compound having from 2 to 30 carbon atoms.

In a particular variation of the method, the mixture comprises unsaturated compounds having from 2 to 8 carbon atoms.

In a further variation of the method, the mixture comprises polyunsaturated hydrocarbons. In certain embodiments, the mixture comprises butadiene.

The unsaturated compounds which are hydroformylated in the process according to the invention further comprise unsaturated carboxylic acid derivatives. In certain embodiments, such unsaturated carboxylic acid derivatives are selected from fatty acid esters.

The method according to the invention is carried out in various embodiments which are disclosed in detail in the embodiments.

The multiphase reaction mixture of the present invention comprises a gas mixture of carbon monoxide and hydrogen as well as one or more unsaturated compounds as described above and is derived from a cracking plant or a catalytic working cracking plant or oligomerization operation, And / or other sources of polyunsaturated carbon compounds, as well as at least one hydroformylation product of such an unsaturated compound as described in the following examples, and in each case as described above &Lt; / RTI &gt;

Figure 1 shows the calculated complex (Ic) where R1 = Me, R2 = Me, R3 = tBu, R4 = OMe and M = Rh.

The complexes of formula Ic and IIc of the present invention are formed in the system during the hydroformylation reaction.

In certain embodiments of the present invention, complexes (Ic) and (IIc) are present with unconjugated bisphosphites.

The hydridocarbonyl complex Ic with rhodium as a metal was characterized using theoretical calculations. The results are shown in Fig.

Structural calculations were performed with BP86 range function and def-SV (P) base set.

Based on the density function theory (DFT), structural calculations were performed on the model structure using a Turbomole program package (R. Ahlrichs, M. Baer, M. Haeser, H. Horn, C. Koelmel , Turbomol V6.3 2011, University of Karlsruhe and Forschungszentrum Karlsruhe GmbH (1989-2007), Turbo Mole, Developed Mogembe (since 2007). Http://www.turbomole.com). Rev. A, 1988, 38, 3098); [J. Am. J. Phys., 1980, 58, 1200; H., Horn and R. Ahlrichs, J. Chem. Phys., 1992, 97, 2571) and the def-SV (P) base set (Perdew, Phys. Rev. B, 1986, 33, 8822) Were used.

Example

Ligand mixture ( 1Ia ) And ( 2IIa ) Synthesis of

Abbreviation:

DM water = demineralized water

CPG = core-pull precision glass

ACN = acetonitrile

EtOAc = ethyl acetate

DMAB = dimethylaminobutane

NMP = N-methylpyrrolidone

OV = oil vacuum

acac = acetylacetonate

NEt ₃ = triethylamine

TIPB = 1,2,4,5-tetraisopropylbenzene

2,2'- Bis (3,5-dimethylphenol) ( 5aa ) Synthesis of

The biphenol (5aa) used as a precursor was prepared by the following synthesis method.

To 500 ml Schlenk with CPG stirrer, middle portion and glass stirrer was added 150 ml of DM water and 1.42 g (0.005 mol) of iron (II) sulfate heptahydrate in 5 ml of cyclohexane and 12.35 g (0.1 mol ) Of 2,4-dimethylphenol were first charged and the mixture was heated to 40 &lt; 0 &gt; C.

In a 100 ml beaker, 25.36 g (0.146 mol) of sodium persulfate was dissolved in 80 ml of DM water. At the start of the reaction, a small portion of the Na ₂ S ₂ O ₈ solution was added to the phenol. Subsequently, a smaller portion of the solution was added every 10 minutes. After 30 minutes, Na ₂ S ₂ O ₈ solution was added.

After a reaction time of 5 hours, 300 ml of cyclohexane and 200 ml of water were added to the reaction solution left to stir for 20 minutes and then transferred to a separating funnel with warming.

The organic phase was removed and concentrated to dryness. The product was obtained in 69% yield (10.6 g).

All subsequent preparations were carried out with a standard Schlenk technique under protective gas. The solvent was dried on a suitable desiccant before use (W. L. F. Armarego (Author), Christina Chai (Author), Butterworth Heinemann (Elsevier, 6th edition, Oxford 2009).

The product was characterized using NMR spectroscopy. Chemical shifts were reported in ppm. ^{The 31} P NMR signal was recorded according to SR _31P = SR _1H ^* (BF _31P / BF _1H ) = SR _1H ^* 0.4048 (Robin K. Harris, Edwin D. Becker, Sonia M. Cabral de Menezes, Pierre Granger, Pure Appl. Chem., 2001, 73, 1795-1818]; [Robin K. Harris, Edwin D. Becker, Sonia M. Cabral de Menezes, Pierre Granger, Roy E. Hoffman and Kurt W. Zilm, Appl. Chem., 2008, 80, 59-84). ³¹ P NMR was used to determine the ratio of the two ligands (ligand 1Ia and ligand 2IIa) relative to each other. The asymmetric ligand (1Ia) was characterized with two signals, but only one in-signal was expected for the symmetric ligand (2IIa).

2,2'- Bis (3,5-dimethylphenol) Of chlorophosphite  synthesis

A fixed 2 l of the sulcan with a magnetic stirrer was charged with 440 ml of phosphorus trichloride first. 120 g of 2,2-bis (3,5-dimethylphenol) was weighed in a second fixed 1 l of Schlenk and 500 ml of anhydrous toluene was added with stirring. The biphenol-toluene suspension was metered in at 63 DEG C over 4 hours with phosphorus trichloride. Upon completion of the addition, the reaction mixture was stirred overnight at temperature. The next morning, the solution was concentrated with warming (45 캜) and the product was obtained in 96.5% yield (153 g). ³¹ P NMR: 175.59 (94.8% 2,2'-bis (3,5-dimethylphenol) chlorophosphite), 4.4% various PCl compounds, 0.8% PH compounds.

Ligand ( 1Ia ) And ( 2IIa ) &Lt; / RTI &gt; of the invention Variation example :

Variant 1: ACN / NEt ₃

38.75 g (0.121 mol) of 2,2'-bis (3,5-dimethylphenyl) chlorophosphite were dissolved in 150 ml of degassed ACN under a protective gas in a 1000 ml Schlenk and heated to 35 ° C . In a second schlenk (500 ml), 20.1 g (0.056 mol) of 3,3'-di-tert-butyl-5,5'-dimethoxy- [1,1'- -Diol was dissolved in 150 ml of degassed ACN and 40.9 ml of degassed triethylamine (0.29 mol) was added with stirring. The biphenol / triethylamine solution was then slowly added dropwise to the chlorophosphite solution. After an additional reaction time of 1 hour, the reaction solution was stirred overnight at 45 &lt; 0 &gt; C.

Subsequently, the solution was filtered and the solid was washed three times with 100 ml warm (45 &lt; 0 &gt; C) ACN. The target product was obtained as a white solid (43.3 g, 86%). ³¹ P NMR (202.4 MHz, toluene-d ₈ ): 142.5 and 140.9 (95.4%) 139.2 (4.6%).

Variation 2: EtOAc / NEt ₃

7.3 g (21.0 mmol) of 2,2'-bis (3,5-dimethylphenyl) chlorophosphite are dissolved in 15 ml of degassed ethyl acetate under a protective gas in a 100 ml Schlenk and heated to 35 & Respectively. In a second schlenk (100 ml), 3.9 g (9.5 mmol) of 3,3'-di-tert-butyl-5,5'-dimethoxy- [1,1'- -Diol was suspended in 7.0 ml of NEt ₃ . Subsequently, the biphenol / triethylamine solution was slowly added dropwise to the chlorophosphite solution within 20 minutes. The solution was stirred at 35 &lt; 0 &gt; C for an additional hour and then at 45 &lt; 0 &gt; C overnight.

The next day, the solution was filtered and the solid was washed three times with ACN. The target product was obtained as a white solid (6.7 g, 78%). ³¹ P NMR (202.4 MHz, toluene-d ₈ ): 142.5 and 140.9 (91.3%), 139.5 (8.7%).

Variant 3: EtOAc / pyridine

In a 250 ml Schlenk, 10.07 g (31.0 mmol) of 2,2'-bis (3,5-dimethylphenyl) chlorophosphite are dissolved in 20 ml of degassed ethyl acetate under protective gas and heated to 45 &lt; Respectively. In a second schlenk (50 ml), 5.54 g (15 mmol) of 3,3'-di-tert-butyl-5,5'-dimethoxy- [1,1'- -Diol were dissolved in 26 ml of ethyl acetate and 5.2 ml of degassed pyridine. Subsequently, the biphenol / pyridine solution was slowly added dropwise to the chlorophosphite solution within 30 minutes. The solution was stirred at 45 &lt; 0 &gt; C overnight.

The next day the solution was filtered and the solid was washed with ACN. The target product was obtained as a white solid (4.2 g, 31%). ³¹ P NMR (202.4 MHz, toluene-d ₈ ): 142.2 and 141.1 (100%).

Variant 4: ACN / DMAB (dimethylaminobutane)

In a 100 ml Schlenk solution, 6 g (19.0 mmol) of 2,2'-bis (3,5-dimethylphenyl) chlorophosphite were dissolved in 20 ml of degassed ACN under protective gas and heated to 35 ° C . In a second schlenk (50 ml), 3.4 g (9.0 mmol) of 3,3'-di-tert-butyl-5,5'-dimethoxy- [1,1'- -Diol was dissolved in 15 ml of dimethylaminobutane (DMAB) and then slowly added dropwise to the chlorophosphite solution. The reaction was allowed to stir at 35 &lt; 0 &gt; C overnight.

The next day, the solution was filtered and the solid was washed twice with ACN. The target product was obtained as a white solid (5.3 g, 66%). ³¹ P NMR (202.4 MHz, toluene-d ₈ ): 142.8 and 141.2 (97.5%), 139.4 (2.5%).

Variation 5: ACN / NMP (N-methylpyrrolidone)

In a 100 ml Schlenk solution, 6 g (19.0 mmol) of 2,2'-bis (3,5-dimethylphenyl) chlorophosphite were dissolved in 20 ml of degassed ACN under protective gas and heated to 35 ° C . In a second schlenk (50 ml), 3.4 g (9.0 mmol) of 3,3'-di-tert-butyl-5,5'-dimethoxy- [1,1'- -Diol was dissolved in 9.4 ml of N-methylpyrrolidone (NMP) and slowly added dropwise to the chlorophosphite solution. The reaction was stirred overnight at 35 &lt; 0 &gt; C.

Subsequently, the solution was filtered and the solid was washed twice with ACN. The target product was obtained as a white solid (3.4 g, 42%). ³¹ P NMR (202.4 MHz, toluene-d ₈ ): 142.2 and 141.0 (96.1%), 139.8 (3.9%).

Variant 6: ACN / diisopropylethylamine

Under a protective gas, 19.4 g (61.0 mmol) of 2,2'-bis (3,5-dimethylphenyl) chlorophosphite were suspended in 75 ml of degassed ACN in a 500 ml Schlenk. 10.5 g (28.5 mmol) of 3,3'-di-tert-butyl-5,5'-dimethoxy- [1,1'-biphenyl] -2,2 ' -Diol were suspended in 75 ml of acetonitrile and 39 ml of diisopropylamine and gradually added to the chlorophosphite solution. The reaction was allowed to stir overnight.

Subsequently, the solution was filtered and the solid washed three times with ACN. The target product was obtained as a white solid (14.6 g, 57%). ³¹ P NMR (202.4 MHz, toluene-d ₈ ): 142.2 and 141.1 (76.8%), 139.1 (23.2%).

Variation 7: Toluene / NEt ₃

7.7 g (24.0 mmol) of 2,2'-bis (3,5-dimethylphenyl) chlorophosphite were dissolved in 15 ml of degassed toluene and heated to 35 ° C under protective gas in a 100 ml Schlenk . In a second Schlenk (50 ml) 3.4 g (9.0 mol) of 3,3'-di-tert-butyl-5,5'-dimethoxy- [1,1'- -Diol was dissolved in 15 ml of dimethylaminobutane (DMAB) and slowly added dropwise to the chlorophosphite solution. The reaction was allowed to stir at 45 &lt; 0 &gt; C for 4 days. After addition of 120 ml of toluene, the solution was then heated to 75 DEG C for 30 minutes.

Subsequently, the solution was filtered, the filtrate was concentrated to dryness and dried. The target product was obtained as a white solid (7.2 g, 88%). ³¹ P NMR (202.4 MHz, toluene-d ₈ ): 142.5 and 140.9 (91.4%), 139.2 (8.6%).

Variant 8: Variation on amount of amines (ACN / NEt ₃ )

A: In a 500 ml Schlenk, 17.81 g (0.073 mol) of 2,2'-bis (3,5-dimethylphenyl) chlorophosphite are added to 60 ml of degassed ACN under protective gas, And heated. In a second schlenk (250 ml), 9.91 g (0.0276 mol) of 3,3'-di-tert-butyl-5,5'-dimethoxy- [1,1'- -Diol was dissolved in 60 ml of degassed ACN and 38.4 ml of degassed triethylamine was added with stirring. This biphenol / triethylamine solution was then slowly added dropwise to the chlorophosphite solution. After an additional reaction time of 1 h, the reaction solution was stirred at 35 &lt; 0 &gt; C overnight.

Subsequently, the solution was filtered and the solid was washed with ACN. The target product was obtained as a white solid (27.8 g, 86%). ³¹ P NMR (202.4 MHz, toluene-d ₈ ): 142.8 and 141.2 (91.6%), 139.4 (8.4%).

B: In a 250 ml Schlenk, 1.57 g (5.1 mmol) of 2,2'-bis (3,5-dimethylphenyl) chlorophosphite are added to 7 ml of degassed ACN under protective gas, And heated. In a second schlenk (100 ml), 0.932 g (2.6 mmol) of 3,3'-di-tert-butyl-5,5'-dimethoxy- [1,1'- -Diol was dissolved in 9 ml of degassed ACN and 2.09 ml of degassed triethylamine was added with stirring. The biphenol / triethylamine solution was then slowly added dropwise to the chlorophosphite solution. After an additional reaction time of 1 h, the reaction solution was stirred at 35 &lt; 0 &gt; C overnight.

Subsequently, the solution was filtered and the solid was washed with ACN. The target product was obtained in 40% yield as a white solid. ³¹ P NMR (202.4 MHz, toluene-d ₈ ): 142.8 and 141.8 (92.4%), 139.3 (7.6%).

Variation 9: Shortened reaction time

A ( 8 h ): EtOAc / NEt ₃

8 g (25.0 mmol) of 2,2'-bis (3,5-dimethylphenyl) chlorophosphite are dissolved in 20 ml of degassed ethyl acetate under a protective gas in a 100 ml Schlenk and heated to 45 ° C. Respectively. In a second Schlenk (50 ml), 4.48 g (12.5 mmol) of 3,3'-di-tert-butyl-5,5'-dimethoxy- [1,1'- biphenyl] -2,2 ' -diol was suspended in ethyl acetate and 8.0 ml of NEt ₃ in 20 ml. Subsequently, the biphenol / triethylamine suspension was slowly added dropwise to the chlorophosphite solution within 30 minutes. The solution was stirred at 45 &lt; 0 &gt; C for 8 hours.

Subsequently, the solution was filtered. The target product was obtained as a white solid (12.26 g, 84.7%). ³¹ P NMR (202.4 MHz, toluene-d ₈ ): 142.2 and 141.1 (88.1), 139.1 (11.9).

B ( 4 h ): EtOAc / NEt ₃

In a 100 ml Schlenk, 10.07 g (31.0 mmol) of 2,2'-bis (3,5-dimethylphenyl) chlorophosphite are dissolved in 20 ml of degassed ethyl acetate under protective gas and heated to 45 & Respectively. In a second schlenk (50 ml), 5.54 g (15 mmol) of 3,3'-di-tert-butyl-5,5'-dimethoxy- [1,1'- - diol were suspended in 26 ml of ethyl acetate and 9.0 ml of NEt _3. Subsequently, the biphenol / triethylamine suspension was slowly added dropwise to the chlorophosphite solution within 30 minutes. The solution was stirred at 45 &lt; 0 &gt; C for 4 hours.

Subsequently, the solution was filtered and the solid was washed twice with ACN. The target product was obtained as a white solid (6.4 g, 47%). ³¹ P NMR (202.4 MHz, toluene-d ₈ ): 142.2 and 141.1 (99.3%), 139.1 (0.7%).

C ( 4 h ): ACN / pyridine

In a 250 ml Schlenk solution, 10 g (31.0 mmol) of 2,2'-bis (3,5-dimethylphenyl) chlorophosphite were dissolved in 40 ml of degassed ACN under protective gas and heated to 45 &lt; . In a second schlenk (50 ml), 5.5 g (15.0 mmol) of 3,3'-di-tert-butyl-5,5'-dimethoxy- [1,1'- -Diol were dissolved in 40 ml of ACN and 8.8 ml of pyridine. The resulting clear biphenol / pyridine solution was then slowly added dropwise to the chlorophosphite solution within 30 minutes. After a reaction time of 4 hours, the solution was filtered and the solid was washed twice with ACN. The target product was obtained as a white solid (8.5 g, 63%). ³¹ P NMR (202.4 MHz, toluene-d ₈ ): 142.2 and 141.1 (98.4%), 139.4 (1.6%).

Variation 10: Low Temperature Experiment (ACN / NEt ₃ )

A : In a 250 ml Schlenk solution, 8.0 g (0.025 mol) of 2,2'-bis (3,5-dimethylphenyl) chlorophosphite are dissolved in 30 ml of degassed ACN under a protective gas, Lt; / RTI &gt; In a second schlenk (100 ml), 4.32 g (0.012 mol) of 3,3'-di-tert-butyl-5,5'-dimethoxy- [1,1'- -Diol was dissolved in 30 ml of degassed ACN and 8.5 ml of degassed triethylamine was added with stirring. The biphenol / triethylamine solution was then slowly added dropwise to the chlorophosphite solution. After an additional reaction time of 1 h, the reaction solution was allowed to gradually warm to room temperature overnight.

Subsequently, the solution was filtered and the solid was washed with cold ACN. The target product was obtained as a white solid (8.9 g, 82%). ³¹ P NMR (202.4 MHz, toluene-d ₈ ): 142.5 and 140.9 (98.4%), 139.4 (1.6%).

Variation 11: Performance at various reaction temperatures (ACN / pyridine)

A : In a 250 ml Schlenk solution, 9.4 g (28.8 mmol) of 2,2'-bis (3,5-dimethylphenyl) chlorophosphite were dissolved in 100 ml of degassed ACN under protective gas. In a second schlenk (100 ml), 5.0 g (14.4 mmol) of 3,3'-di-tert-butyl-5,5'- dimethoxy- [1,1'- biphenyl] -2,2 ' -Diol were suspended in 8.8 ml of pyridine. The biphenol / pyridine solution was then slowly added dropwise to the chlorophosphite solution within 1.5 hours. The solution was stirred at room temperature for a further 2 hours and then at 60 &lt; 0 &gt; C overnight.

Subsequently, the solution was filtered and the solid was washed twice with ACN. The target product was obtained as a white solid (9.5 g, 73%). ³¹ P NMR (202.4 MHz, toluene-d ₈ ): 142.8 and 141.2 (90%), 139.5 (10%).

B : In a 250 ml Schlenk solution, 10 g (31.0 mmol) of 2,2'-bis (3,5-dimethylphenyl) chlorophosphite are dissolved in 40 ml of degassed ACN under protective gas, And heated. In a second schlenk (50 ml), 5.5 g (15.0 mmol) of 3,3'-di-tert-butyl-5,5'-dimethoxy- [1,1'- -Diol were dissolved in 40 ml of ACN and 8.8 ml of pyridine. The resulting clear biphenol / pyridine solution was then slowly added dropwise to the chlorophosphite solution within 30 minutes. The solution was stirred at 45 &lt; 0 &gt; C overnight. The next morning, the solution was filtered and the solid was washed twice with ACN. The target product was obtained as a white solid (9.5 g, 72%). ³¹ P NMR (202.4 MHz, toluene-d ₈ ): 142.2 and 141.1 (89.9%), 139.1 (10.1%).

Comparative Example, Variant 12: "1-Port Synthesis"

8.45 g (0.0335 mol) of 2,2'-bis (3,5-dimethylphenol) and 5.95 g (0.0166 mol) of 3,3 ', 5'- dimethylphenol were suspended in 50 ml of anhydrous toluene with stirring in a fixed 250 ml Schlenk. Di-tert-butyl-5,5'-dimethoxy- [1,1'-biphenyl] -2,2'-diol. 7.1 g (0.051 mol) of phosphorus trichloride and 0.1 ml (0.001 mol) of pyridine were then successively added to the suspension at 0 &lt; 0 &gt; C and the suspension was allowed to room temperature (RT) within 60 min. Subsequently, the reaction mixture was heated to 35 &lt; 0 &gt; C and stirred at this temperature overnight.

In the morning, OV was used at RT to remove excess phosphorus trichloride and solvent. Thereafter, 25 ml of degassed ACN was added with stirring, and the solution was cooled to 0 &lt; 0 &gt; C. A second schlenk (50 ml) was charged with 25 ml of degassed ACN first and 10.2 g = 14 ml (0.1 mol) of triethylamine were added with stirring. The resulting solution was added dropwise to the cooled reaction mixture within 45 min. The mixture was then warmed to RT overnight with stirring. In the morning, the solids were filtered off and washed with 2 x 25 ml of degassed ACN. The desired target product was obtained in 77% yield (13 g). ³¹ P NMR (202.4 MHz, toluene-d ₈ ): 142.2 and 141.1 (96.4%), 139.2 (3.6%).

Effect of base / base mixture

Typical synthesis methods

Under protective gas, 38.75 g (0.121 mol) of 2,2'-bis (3,5-dimethylphenyl) chlorophosphite were dissolved in 150 ml of degassed ACN in 1000 ml Schlenk and heated to 45 ° C . In a second schlenk (500 ml), 20.1 g (0.056 mol) of 3,3'-di-tert-butyl-5,5'-dimethoxy- [1,1'- -Diol was dissolved in 150 ml of degassed ACN and the appropriate base (the amount used was based on the chlorophosphite) was added with stirring. The biphenol / base solution was then slowly added dropwise to the chlorophosphite solution. After an additional reaction time of 1 hour, the reaction solution was stirred overnight at 45 &lt; 0 &gt; C. (Other temperatures or reaction times can be found in the table.)

Subsequently, the solution was filtered and the solid was washed with 100 ml of warm (45 캜) ACN. Compound la was obtained as a white solid (yield (%)). ³¹ P NMR (202.4 MHz, toluene-d ₈ ): 142.5 and 140.9 (ligand 1a (%)), 139.2 (ligand 2a (%)).

Synthetic route:

A) Pyridine and derivatives

DMAP = dimethylaminopyridine

^* : Experiment at 0 ° C

^** : Experiment at 50 ° C

^*** : Extended reaction time (5 days)

^**** : Immediate addition instead of gradual ^load

^# : Reaction at 0 ° C

^## : Reaction at 3-7 ° C

^### : Reaction at 45 ° C

As is evident in Table 3, it was possible to control the isomeric distribution of the two structural isomers (1a) and (2a) by selecting a corresponding amount of base or base. For example, it was possible to obtain a 1: 1 mixture of two isomers (1a) and (2a) by using DMAP as the base at the lower temperature.

B) Various alkylamines

NEt ₃ : Triethylamine

DMAB: Dimethylaminobutane

n.d .: Not measured

As clearly evident from Table 4, the choice of the trialkylamine as the base gives the asymmetric isomer (1a) as a major component with a purity of > 90% and the isomeric mixture in which the symmetric isomer (2a) constitutes the corresponding subcomponent It was possible.

C) Various base mixtures

NBu ₃ : triethylamine

DMAP: Dimethylaminopyridine

pyr: pyridine

As clearly evident in Table 5, it was possible to control the isomeric distribution of the two structural isomers (1a) and (2a) by using a base mixture and a correspondingly positive base.

Thus, it was possible to affect the isomeric distribution of the two structural isomers (1a) and (2a) by selecting a base or base mixture to be used such that one isomer is present as the main component. By selecting the trialkylamine as a base, it was possible to obtain an isomeric mixture wherein the asymmetric isomer (1a) is present as a major component in a purity of> 90% and the symmetric isomer (2a) constitutes the corresponding subcomponent. Since this mixture also exhibits very good overall performance in hydroformylation, it is possible to eliminate further purification steps.

Ligand ( 3Ia Synthesis of the present invention of general formula

Phosphite  ( 7) of  synthesis

A fixed 1000 ml Schlenk was charged with 400 ml of anhydrous toluene first, and 8.9 ml (0.1 mol) phosphorus trichloride was added using a syringe and the mixture was cooled to 0 占 폚.

A solution of 71.6 g (0.2 mol) of 3,3'-di-tert-butyl-2,2'-dihydroxy-5,5'-dimethoxybiphenyl in 500 ml of Schlenk was weighed out and 325 ml of anhydrous toluene and Was dissolved in 49 ml (0.35 mol) of anhydrous triethylamine.

The biphenol / Et ₃ N / toluene suspension was then added dropwise to the PCl ₃ / toluene solution cooled to 0 ° C within 2.5 hours and allowed to react overnight at RT.

The next morning, the solid formed was filtered off, washed repeatedly with anhydrous toluene, and the filtrate was concentrated to dryness. To obtain a white solid, ACN was used for further washing. Thus, the target product was obtained in 79.5% yield (59.1 g).

Diorganophosphite Dichlorophosphite  ( 8) of  synthesis

42 g (0.056 mol) of phosphite (7) were weighed in a fixed 250 ml Schlenk and 275 ml anhydrous toluene and 17 ml (0.168 mol) anhydrous triethylamine were added with stirring.

First, 200 ml of anhydrous toluene was first charged to a second 1000 ml Schlenk, followed by 14.76 ml (0.169 mol) phosphorus trichloride. Subsequently, the prepared phosphite / amine / toluene solution was added dropwise to the phosphorus trichloride / toluene solution within 30 minutes at RT, with vigorous stirring. Upon completion of the addition, the reaction mixture was heated to 80 &lt; 0 &gt; C for 6 hours and allowed to RT overnight.

The next morning, the mixture was filtered, the solid was washed with 50 ml of anhydrous toluene, and the filtrate was concentrated to dryness. The product was obtained in 89% yield (45.6 g).

Ligand ( 3Ia ) Of the present invention

In the glove box, 3.08 g (0.0036 mol) of diorganophosphite dichlorophosphite (8) was weighed in a fixed 100 ml Schlenk and then dissolved in 35 ml anhydrous toluene.

In a second fixed 250 ml Schlenk, 0.872 g (0.0036 mol) of 2,2'-bis (3,5-dimethylphenol) and 1.09 g (0.01 mol) of anhydrous triethylamine were dissolved in 35 ml of toluene .

The diorganophosphite dichlorophosphite (8) was then slowly and continuously added dropwise to the biphenyl-triethylamine solution with vigorous stirring at room temperature. Subsequently, the reaction mixture was stirred overnight.

For work-up, the solids formed the next morning were filtered off and washed twice with 5 ml anhydrous toluene. The resulting filtrate was then concentrated to dryness. The target product was obtained as a white solid (2.59 g; 71%).

Ligand ( 4IIa Synthesis of the present invention of general formula

3,3'- tert Butyl-2,2'-dihydroxy-5,5'- Dimethoxybiphenyl Chlorophosphite  (6ba)

35.8 g (0.1 mol) of 3,3'-tert-butyl-2,2'-dihydroxy-5,5'-dimethoxybiphenol were weighed in 500 ml of Schlenk and 42.3 ml ) Of degassed triethylamine and 250 ml of anhydrous toluene.

A second, fixed 1 L sulink was charged with 8.8 ml (0.1 mol) of PCl ₃ in 300 ml of anhydrous toluene and cooled to 0 占 폚. The prepared phenol / amine solution was then carefully added dropwise to the PCl ₃ / toluene solution with vigorous stirring.

After addition, the solution was warmed to RT overnight. The following morning, the solid formed was filtered off and the solvent was concentrated to dryness. The product was obtained as a honey-like residue in 56% yield (27.5 g).

Ligand ( 4IIa ) Of the present invention

9.79 g (0.022 mol) of chlorophosphite (6ba) was weighed in a fixed 250 ml Schlenk and then dissolved in 75 ml anhydrous toluene.

2.66 g (0.011 mol) of 2,2'-bis (3,5-dimethylphenol) and 2.46 g (0.022 mol) of potassium tert-butoxide were weighed in a further fixed 100 ml Schlenk and 70 ml Of anhydrous toluene.

At RT, the biphenol / potassium tert-butoxide mixture was slowly and uniformly added dropwise to the initially charged chlorophosphite solution while stirring at RT. Subsequently, the mixture was filtered through Celite. The solution was concentrated and the remaining residue was washed with 50 ml of anhydrous acetonitrile. The target product was obtained in 25.5% yield (2.76 g).

Hydroformylation  Procedure for experiment

Experiment Description - General

Experiments were performed in a 100 ml autoclave from Parn Instruments. The autoclave was equipped with an electric heater. The mass flow meter and pressure regulator were used to maintain the pressure constant. During the experiment, the syringe pump was used to inject precisely defined amounts of reactants under reaction conditions. Capillary lines and HPLC valves were used to take samples during the experiment, which could be analyzed using both GC and LC-MS analyzes.

Hydroformylation ^[a] in  Ligand ( 1Ia ) And ( 2IIa ) &Lt; / RTI &gt; Results of the present invention for testing of various compound mixtures:

^* Invention

(a) Condition: cis-2-butene, Rh (acac) (CO) ₂ ([Rh] = 95 ppm), L / Rh = 6: 1, 40 ml of toluene, / H ₂ (1: 1) and 1,2,4,5-tetraisopropylbenzene as internal GC standard. [b] GC analysis using 1,2,4,5-tetraisopropylbenzene as internal GC standard. # Additional subcomponents, including non-converted chlorophosphites, present in relatively large amounts. The desired composition of both ligands (1Ia) and (2IIa) is present at a purity of only 30% in a mixture with other components / impurities.

In a comparison of the results of hydroformylation of the various ligand mixtures (Table 6, item 2-6) and the pure ligand (lla) (Table 6, item 1) of ligands lla and llaa, Selectivity and yield. Even when a ligand mixture (Table 6, item 7) in which the ligand (lla) was present at only about 30% purity was used, very good yield and selectivity were still produced. By using a mixture of bisphosphite compounds composed of such ligands (1Ia) and (2IIa), the technical object was thus completely achieved and the corresponding aldehyde was obtained in good to very good yield and selectivity.

Thus, it was also found feasible to use a ligand mixture in the hydroformylation reaction.

Hydroformylation ^[a] in  Ligand ( 1Ia ), ( 3Ia ) And ( 4IIa ) &Lt; / RTI &gt; Results of the present invention for testing of various compound mixtures:

^* Invention

(a) Condition: cis-2-butene, Rh (acac) (CO) ₂ , toluene, compound 11, 120 ° C, 20 bar CO / H ₂ 4,5-tetraisopropylbenzene or mesitylene. [b] GC analysis using 1,2,4,5-tetraisopropylbenzene or mesitylene as internal GC standard. [c] pentanal selectivity and yield [%]. [d] Aldehyde yield [%]. [e] Ratio of two ligands normalized to 100%.

Pure ligands (3Ia) and (4IIa) (Table 7, items 1 and 2) exhibited good pentane selectivity and yield. However, it was also possible to use various ligand mixtures (Table 7, items 3-7) of ligands (3Ia) and (4IIa) as well as pure ligands.

Experiment explanation - Expansion experiment

Experiments were performed in a 100 ml autoclave from Parr Instruments. The autoclave was equipped with an electric heater. The mass flow meter and pressure regulator were used to maintain the pressure constant. During the experiment, the syringe pump was used to inject precisely defined amounts of reactants under reaction conditions. Capillary lines and HPLC valves were used to take samples during the experiment, which could be analyzed using both GC and LC-MS analyzes.

Rh precursor (Rh (acac) (CO) ₂ ) and a ligand or ligand mixture were first charged to 40 ml of isononyl benzoate in an autoclave. The Rh concentration was 100 ppm based on the total reaction mixture used. The excess ligand used was 4: 1 in terms of moles based on rhodium.

Compound (11) was added as an amine as a stabilizer at a ratio of 2: 1 to the ligand. As a GC standard, 0.5 g of 1,2,4,5-tetraisopropylbenzene was added.

The reaction temperature was 120 占 폚. The reaction pressure was the synthesis gas of _{20 bar (H 2: CO =} 50:50 % by volume).

As the olefin, 4 ml of cis-2-butene was metered in at intervals of about one day each time using a syringe pump. GC samples were taken after 1, 2, 4 hours and before the next metered addition.

The following ligands were studied in relation to their stability:

The ligand (2Ia) ( ³¹ P NMR: L1Ia = 91% and L2IIa = 9%) were also studied:

And a mixture of ligand (10IIa) and ligand (9Ia) ( ³¹ P NMR: L10IIa = 75% and L9Ia = 25%

Results - Expansion Experiment

The relative activity was determined by the ratio of k to the k value at time zero (the beginning of the reaction) in the reaction, k, and the relative decrease in activity over the duration of the experiment is described.

The primary k values were obtained from plots of (-ln (1-conversion)) over time.

^* Invention

The reduction in catalytic activity of the bifepoose ligand and the ligand (10IIa) was much more pronounced than the ligand (11a) (Table 8; items 8-11) (Table 8; items 1-4, 16-19). It is noted that the relative activity of the ligand (I Ia) after almost two times the reaction time (Table 8; item 11) was still more than twice as large as the other two ligands after half reaction time (Table 5; items 4 and 19) Respectively. In addition, the n / i ratio for the catalyst with ligand 10IIa was still very high.

When the pure ligand (11a) was compared with the mixture of the ligand (11a) + (2IIa) (Table 8; items 8-11, 12-15), the mixture was found to be comparable to the pure ligand (11a) after a running time of 117 hours Activity and selectivity. The mixture of ligand (10IIa) + (9Ia) exhibited much poorer selectivity than the mixture of pure ligand (10IIa) and also ligand (lla) + (IIla) from the beginning (Table 8; And 16-19).

The addition of the asymmetric ligand 9Ia to the symmetric ligand 10IIa resulted in a sharp drop in selectivity (Table 8; items 5-7). (See Rhodium-catalyzed Hydroformylation, ed. By P. W. N. M. van Leeuwen and C. Claver, Kluwer Academic Publishers 2006, AA Dordrecht, NL). In complete contrast, the asymmetric ligand (lla) as a pure substance and as a mixture with the ligand (2IIa) (Table 8; items 8-11, 12-15) were all surprisingly characterized by excellent shelf life and very good selectivity. It has also been found that such a mixture of the structured ligand compounds (1Ia) and (2IIa) can also be used directly from the synthesis without further complicated purification operations.

Results of the present invention - Variation example

For subsequent experiments, the following mixtures were studied: ligand (1Ia) + ligand (2IIa) ( ³¹ P NMR: LIla = 91% + LI2a = 9%).

Example 1

In a 100 ml autoclave from Parr Instruments, 4.8 g of propene was hydroformylated at 120 &lt; 0 &gt; C and 30 bar. As a precursor, 0.0038 g of Rh (acac) (CO) ₂ was _first charged into 43.08 g of toluene. As the ligand, 0.0708 g of the ligand mixture described above ( ³¹ P NMR: LIla = 91% + LI2a = 9%) was used in the catalyst mixture solution. 0.0401 g of compound (11) was added as an organic amine and 0.5033 g of TIPB was added as a GC standard. After reaching the expected reaction temperature, the reactants were metered thereto.

During the reaction, the pressure was kept constant by adjusting the syngas using a mass flow meter. Samples were taken from the reaction mixture after 20 hours. 88.4 mol% butanal, 6.48 mol% 2-methylpropanal and 2.79 mol% propane were formed. The position selectivity for n-butanol was 93.2%.

Example 2

In a 100 ml autoclave from Parr Instruments, 6.7 g of cis-2-butene was hydroformylated at 120 &lt; 0 &gt; C and 20 bar. As a precursor, 0.0053 g of Rh (acac) (CO) ₂ was _first charged into 43.48 g of toluene. As the ligand, 0.0671 g of the ligand mixture described above ( ³¹ P NMR: LIla = 91% + LI2a = 9%) was used in the catalyst mixture solution. 0.0381 g of compound (11) was added as an organic amine and 0.5099 g of TIPB was added as a GC standard. After reaching the expected reaction temperature, the reactants were metered thereto.

During the reaction, the pressure was kept constant by adjusting the syngas using a mass flow meter. Samples were taken from the reaction mixture after 20 hours. 84.6 mol% pentane, 5.70 mol% 2-methylbutanal and 3.43 mol% n-butane were formed. The position selectivity for n-pentanal was 93.7%.

Example 3

In a 100 ml autoclave from Parr Instruments, 6.7 g of 1-butene was hydroformylated at 120 &lt; 0 &gt; C and 20 bar. As a precursor, 0.0052 g of Rh (acac) (CO) ₂ was first charged to 43.08 g of toluene. As the ligand, 0.0694 g of the ligand mixture described above ( ³¹ P NMR: LIla = 91% + LI2a = 9%) was used in the catalyst mixture solution. 0.0378 g of compound (11) was added as an organic amine and 0.5052 g of TIPB was added as a GC standard. After reaching the expected reaction temperature, the reactants were metered thereto.

During the reaction, the pressure was kept constant by adjusting the syngas using a mass flow meter. Samples were taken from the reaction mixture after 20 hours. 86.5 mol% pentane, 5.08 mol% 2-methylbutane and 3.23 mol% n-butane were formed. The position selectivity for n-pentanal was 98.9%.

Example 4

In a 100 ml autoclave from Parr Instruments, 6.7 g of isobutene was hydroformylated at 120 &lt; 0 &gt; C and 20 bar. As a precursor, 0.0051 g of Rh (acac) (CO) ₂ was _first charged into 42.1 g of toluene. As the ligand, 0.0678 g of the ligand mixture described above ( ³¹ P NMR: LIla = 91% + LI2a = 9%) was used in the catalyst mixture solution. 0.0369 g of compound (11) was added as an organic amine and 0.4937 g of TIPB was added as a GC standard. After reaching the expected reaction temperature, the reactants were metered thereto.

During the reaction, the pressure was kept constant by adjusting the syngas using a mass flow meter. Samples were taken from the reaction mixture after 20 hours. 64.0 mol% 3-methylbutanal, 0.07 mol% pseudoaldehyde and 2.92 mol% isobutane were formed.

Example 5

In a 100 ml autoclave from Parr Instruments, 2.9 mol% of isobutane, 9.9 mol% of n-butane, 28.7 mol% of 1-butene, 43.5 mol% of isobutene, 14.6 mol% of 2-butene and 0.2 mol 7.4 g of a C-4 mixture having a composition of 1, 3-butadiene was hydroformylated at 120 &lt; 0 &gt; C and 20 bar. As a precursor, 0.0048 g of Rh (acac) (CO) ₂ was first charged into 41.49 g of toluene. As the ligand, 0.0681 g of the ligand mixture described above ( ³¹ P NMR: LIla = 91% + LI2a = 9%) was used in the catalyst mixture solution. 0.0367 g of compound (11) was added as an organic amine and 0.5027 g of TIPB was added as a GC standard. After reaching the expected reaction temperature, the reactants were metered thereto.

During the reaction, the pressure was kept constant by adjusting the syngas using a mass flow meter. Samples were taken from the reaction mixture after 20 hours. The product contained 32.7% of 3-methylbutane (75.2 mol% of isobutene conversion), 39.44 mol% of n-pentanol and 2.18 mol% of 2-methylbutane (conversion of butene to 78.1 mol% Position selectivity 94.8%). As the hydrogenation product, 4.13 mol% of isobutane and 9.95 mol% of n-butane were found in the product.

Example 6

In a 100 ml autoclave from Parr Instruments, 5.9 mol% of isobutane, 15.6 mol% of n-butane, 52.9 mol% of 1-butene, 0.1 mol% of isobutene, 24.8 mol% of 2-butene and 0.5 mol 7.0 g of a C-4 mixture having a composition of 1, 3-butadiene was hydroformylated at 120 &lt; 0 &gt; C and 20 bar. As a precursor, 0.0054 g of Rh (acac) (CO) ₂ was first charged to 46.93 g of toluene. As the ligand, 0.0755 g of the ligand mixture described above ( ³¹ P NMR: LIla = 91% + LI2a = 9%) was used in the catalyst mixture solution. 0.0412 g of compound (11) was added as an organic amine and 0.5467 g of TIPB was added as a GC standard. After reaching the expected reaction temperature, the reactants were metered thereto.

During the reaction, the pressure was kept constant by adjusting the syngas using a mass flow meter. Samples were taken from the reaction mixture after 20 hours. The product contained 0.17 mol% of 3-methylbutanal, 70.31 mol% of n-pentanal and 4.20 mol% of 2-methylbutanal (93.9 mol% of butene conversion and 94.4% of position selectivity to n-pentanal) Respectively. As the hydrogenation product, 5.52 mol% of isobutane and 18.1 mol% of n-butane were found in the product.

Example 7

In a 100 ml autoclave from Parr Instruments, 5.9 mol% of isobutane, 22.0 mol% of n-butane, 45.5 mol% of 1-butene, 2.1 mol% of isobutene, 17.1 mol% of 2-butene and 0.2 mol 5.0 g of a C-4 mixture having a composition of 1, 3-butadiene was hydroformylated at 120 &lt; 0 &gt; C and 20 bar. As precursor, first, 00044 g of Rh (acac) (CO) ₂ was charged into 37.96 g of toluene. As the ligand, 0.0611 g of the ligand mixture described above ( ³¹ P NMR: LIla = 91% + LI2a = 9%) was used in the catalyst mixture solution. 0.0333 g of compound (11) was added as an organic amine and 0.4422 g of TIPB was added as a GC standard. After reaching the expected reaction temperature, the reactants were metered thereto.

During the reaction, the pressure was kept constant by adjusting the syngas using a mass flow meter. Samples were taken from the reaction mixture after 20 hours. The product contained 1.52 mol% of 3-methyl butanal (72.1 mol% of isobutene conversion), 63.2 mol% of n-pentanol and 3.13 mol% of 2-methyl butanal (95.6 mol% of butene conversion, 95.3% for position selectivity). As the hydrogenation product, 5.41 mol% of isobutane and 23.89 mol% of n-butane were found in the product.

Example 8

In a 100 ml autoclave from Parr Instruments, 3.4 mol% of isobutane, 13.0 mol% of n-butane, 47.3 mol% of 1-butene, 13.9 mol% of isobutene, 21.6 mol% of 2-butene and 0.4 mol 6.4 g of a C-4 mixture having a composition of 1, 3-butadiene was hydroformylated at 120 &lt; 0 &gt; C and 20 bar. As a precursor, 0.0052 g of Rh (acac) (CO) ₂ was _first charged into 44.95 g of toluene. As the ligand, 0.0704 g of the ligand mixture described above ( ³¹ P NMR: Li1a = 91% + Li2a = 9%) was used in the catalyst mixture solution. 0.0387 g of compound (11) was added as an organic amine and 0.5318 g of TIPB was added as a GC standard. After reaching the expected reaction temperature, the reactants were metered thereto.

During the reaction, the pressure was kept constant by adjusting the syngas using a mass flow meter. Samples were taken from the reaction mixture after 20 hours. The product contained 9.93 mol% of 3-methyl butanal (71.7 mol% of isobutene conversion), 62.6 mol% of n-pentanol and 2.98 mol% of 2-methyl butanal (95.6 mol% of butene conversion, 95.5% for position selectivity). As the hydrogenation product, 3.59 mol% of isobutane and 15.41 mol% of n-butane were found in the product.

Example 9

In a 100 ml autoclave from Parn Instruments, a mixture of 0.1 mol% of isobutane, 27.6 mol% of n-butane, 27.9 mol% of 1-butene, 0.1 mol% of isobutene and 44.0 mol% of 2-butene 6.8 g of the C-4 mixture was hydroformylated at 120 &lt; 0 &gt; C and 20 bar. As a precursor, 0.0051 g of Rh (acac) (CO) ₂ was first charged into 42.29 g of toluene. As the ligand, 0.0681 g of the ligand mixture described above ( ³¹ P NMR: LIla = 91% + LI2a = 9%) was used in the catalyst mixture solution. 0.0371 g of compound (11) was added as an organic amine and 0.4960 g of TIPB was added as a GC standard. After reaching the expected reaction temperature, the reactants were metered thereto.

During the reaction, the pressure was kept constant by adjusting the syngas using a mass flow meter. Samples were taken from the reaction mixture after 20 hours. The product contained 60.45 mol% of n-pentanal and 3.51 mol% of 2-methyl butanal (92.8 mol% of butene conversion, 94.5% of position selectivity to n-pentanal). As the hydrogenation product, 0.1 mol% of isobutane and 28.8 mol% of n-butane were found in the product.

Example 10

In a 100 ml autoclave from Parr Instruments, 6.8 g of a C-4 mixture having a composition of 63.6 mol% n-butane, 1.0 mol% 1-butene and 35.8 mol% 2-butene was heated at 120 &Lt; / RTI &gt; As a precursor, 0.0049 g of Rh (acac) (CO) ₂ was _first charged into 40.42 g of toluene. As the ligand, 0.0651 g of the ligand mixture described above ( ³¹ P NMR: LIla = 91% + LI2a = 9%) was used in the catalyst mixture solution. 0.0354 g of compound (11) was added as an organic amine and 0.4740 g of TIPB was added as a GC standard. After reaching the expected reaction temperature, the reactants were metered thereto.

During the reaction, the pressure was kept constant by adjusting the syngas using a mass flow meter. Samples were taken from the reaction mixture after 20 hours. The product contained 27.76 mol% of n-pentanal and 2.14 mol% of 2-methyl butanal (81.0 mol% of butene conversion and 92.8% of position selectivity to n-pentanal). As the hydrogenation product, 65.0 mol% n-butane was found in the product.

Example 11

In a 100 ml autoclave from Parr Instruments, 6.8 trans-2-butene was hydroformylated at 120 &lt; 0 &gt; C and 20 bar. As a precursor, 0.0054 g of Rh (acac) (CO) ₂ was first charged to 43.78 g of toluene. As the ligand, 0.0696 g of the ligand mixture described above ( ³¹ P NMR: LIla = 91% + LI2a = 9%) was used in the catalyst mixture solution. 0.0370 g of compound (11) was added as an organic amine, and 0.5121 g of TIPB was added as a GC standard. After reaching the expected reaction temperature, the reactants were metered thereto.

During the reaction, the pressure was kept constant by adjusting the syngas using a mass flow meter. Samples were taken from the reaction mixture after 20 hours.

The product contained 85.4 mol% n-pentanol and 5.95 mol% 2-methylbutanol (93.4% selectivity for n-pentanol). As the hydrogenation product, 3.99 mol% n-butane was found in the product.

Example 12

In a 100 ml autoclave from Parr Instruments, 1.5 mol% propane, 0.8 mol% propene, 28.1 mol% isobutane, 8.1 mol% n-butane, 16.4 mol% 1-butene, 16.9 mol% 6.0 g of a hydrocarbon mixture from a catalytic cracking plant having a composition of isobutene, 28.2 mol% of 2-butene, 0.5 mol% of 1,3-butadiene and C5 olefins and a fraction of hydrocarbons was hydroformed at 120 DEG C and 20 bar . As a precursor, 0.0046 g of Rh (acac) (CO) ₂ was first charged into 39.43 g of toluene. As the ligand, 0.0672 g of the ligand mixture described above ( ³¹ P NMR: LIla = 91% + LI2a = 9%) was used in the catalyst mixture solution. 0.0331 g of compound (11) was added as an organic amine and 0.4665 g of TIPB was added as a GC standard. After reaching the expected reaction temperature, the reactants were metered thereto. During the reaction, the pressure was kept constant by adjusting the syngas using a mass flow meter. Samples were taken from the reaction mixture after 20 hours.

The product contained 1.2 mol% propane, 0.68 mol% butane, 26.9 mol% isobutane, 9.66 mol% n-butane, 12.66 mol% 3-methylbutane (74.8% isobutene conversion), 39.5 mol % Pentane, 2.07 mol% 2-methylbutane (n-butene conversion: 97.9%, position selectivity to n-pentanal: 95.0%).

Example 13

In a 100 ml autoclave from Parr Instruments, 5.8 g of 1,3-butadiene was hydroformylated at 120 &lt; 0 &gt; C and 20 bar. As a precursor, 0.0048 g of Rh (acac) (CO) ₂ was first charged into 41.19 g of toluene. As the ligand, 0.0677 g of the ligand mixture described above ( ³¹ P NMR: LIla = 91% + LI2a = 9%) was used in the catalyst mixture solution. 0.0364 g of compound (11) was added as an organic amine and 0.4991 g of TIPB was added as a GC standard. After reaching the expected reaction temperature, the reactants were metered thereto. During the reaction, the pressure was kept constant by adjusting the syngas using a mass flow meter. Samples were taken from the reaction mixture after 20 hours.

The product contained 0.26 mol% n-butane, 14.25% n-butene, 16.65% aldehyde and 9.68 mol% 4-vinylcyclohexene. The total conversion of 1,3-butadiene was 42.4%.

Example 14

In a 100 ml autoclave from Parr Instruments, 1.8 g of ethene was hydroformylated at 120 &lt; 0 &gt; C and 50 bar. As a precursor, 0.0050 g of Rh (acac) (CO) ₂ was _first charged into 42.68 g of toluene. As the ligand, 0.0668 g of the ligand mixture described above ( ³¹ P NMR: LIla = 91% + LI2a = 9%) was used in the catalyst mixture solution. 0.0363 g of compound (11) was added as an organic amine and 0.5095 g of TIPB was added as a GC standard. After reaching the expected reaction temperature, the reactants were metered thereto. During the reaction, the pressure was kept constant by adjusting the syngas using a mass flow meter. Samples were taken from the reaction mixture after 20 hours. The conversion to propanol was 98.7%.

Example 15

In a 100 ml autoclave from Parr Instruments, 5.74 g of methyl oleate was hydroformylated at 120 &lt; 0 &gt; C and 20 bar. As a precursor, 0.0049 g of Rh (acac) (CO) ₂ was _first charged into 42.00 g of toluene. As the ligand, 0.0665 g of the ligand mixture described above ( ³¹ P NMR: LIla = 91% + LI2a = 9%) was used in the catalyst mixture solution. 0.0345 g of compound (11) was added as an organic amine and 0.4956 g of TIPB was added as a GC standard. After reaching the expected reaction temperature, the reactants were metered thereto. During the reaction, the pressure was kept constant by adjusting the syngas using a mass flow meter. Samples were taken from the reaction mixture after 20 hours. ^{From the 1} H and ¹³ C NMR spectra, an aldehyde yield of 43.3 mol% was calculated. The position selectivity for the terminal aldehyde was 22.2 mol%. The double bond content was 36.3 mol%.

For subsequent experiments, the combination of ligands (3Ia) and (4IIa) and (3Ia) and (4IIa) was studied.

Example 16

In a 100 ml autoclave from Parr Instruments, 6.0 g of cis-2-butene was hydroformylated at 120 &lt; 0 &gt; C and 20 bar. As precursor, 0.0049 g of Rh (acac) (CO) ₂ was _first charged to 44.38 g of toluene. As the ligand, 0.0783 g of ligand (3Ia) was used in the catalyst mixture solution. 0.0392 g of compound (11) was added as an organic amine and 0.4981 g of TIPB was added as a GC standard. After reaching the expected reaction temperature, the reactants were metered thereto.

During the reaction, the pressure was kept constant by adjusting the syngas using a mass flow meter. Samples were taken from the reaction mixture after 12 hours. 53.2 mol% of pentanal, 16.6 mol% of 2-methylbutanal and 3.19 mol% of n-butane were formed. The position selectivity for n-pentanal was 76.2%.

Example 17

In a 100 ml autoclave from Parr Instruments, 5.8 g of cis-2-butene was hydroformylated at 120 &lt; 0 &gt; C and 20 bar. As a precursor, first, 0.006 g of Rh (acac) (CO) ₂ was charged to 44.3 g of toluene. As the ligand, 0.0907 g of the ligand (4IIa) was used in the catalyst mixture solution. 0.0432 g of compound (11) was added as an organic amine and 1.7624 g of mesitylene was added as a GC standard. After reaching the expected reaction temperature, the reactants were metered thereto. During the reaction, the pressure was kept constant by adjusting the syngas using a mass flow meter. Samples were taken from the reaction mixture after 12 hours. An aldehyde yield of 61.8 mol% was found. The position selectivity for n-pentanal was 76.2 mol%. The proportion of n-butane was 3.2%.

Example 18

In a 100 ml autoclave from Parr Instruments, 6.4 g of cis-2-butene was hydroformylated at 120 &lt; 0 &gt; C and 20 bar. As a precursor, 0.0047 g of Rh (acac) (CO) ₂ was _first charged into 41.71 g of toluene. As the ligand, 0.0674 g of ligand (3Ia) and 0.0075 g of ligand (4IIa) (molar ratio of L3Ia: L4IIa: Rh = 3.7: 0.41: 1) were used in the catalyst mixture solution. 0.0346 g of compound (11) was added as an organic amine and 1.8862 g of mesitylene was added as a GC standard. After reaching the expected reaction temperature, the reactants were metered thereto.

During the reaction, the pressure was kept constant by adjusting the syngas using a mass flow meter. Samples were taken from the reaction mixture after 12 hours. 43.9 mol% of pentanal, 13.0 mol% of 2-methylbutanal and 2.66 mol% of n-butane were formed. The position selectivity for n-pentanal was 77.2%.

Example 19

In a 100 ml autoclave from Parr Instruments, 6.3 g of cis-2-butene was hydroformylated at 120 &lt; 0 &gt; C and 20 bar. As a precursor, 0.0050 g of Rh (acac) (CO) ₂ was first charged into 41.17 g of toluene. As the ligand, 0.0581 g of the ligand (3Ia) and 0.0211 g of the ligand (4IIa) (molar ratio of L3Ia: L4IIa: Rh = 2.96: 1.07: 1) were used in the catalyst mixture solution. 0.0352 g of compound (11) was added as an organic amine, and 1.7344 g of mesitylene was added as a GC standard. After reaching the expected reaction temperature, the reactants were metered thereto.

During the reaction, the pressure was kept constant by adjusting the syngas using a mass flow meter. Samples were taken from the reaction mixture after 12 hours. 46.0 mol% pentane, 17.5 mol% 2-methylbutanal and 2.46 mol% n-butane were formed. The position selectivity for n-pentanal was 72.4%.

Example 20

In a 100 ml autoclave from Parr Instruments, 6.2 g of cis-2-butene was hydroformylated at 120 &lt; 0 &gt; C and 20 bar. As a precursor, 0.0055 g of Rh (acac) (CO) ₂ was _first charged into 43.59 g of toluene. As the ligand, 0.0389 g of the ligand (3Ia) and 0.0388 g of the ligand (4IIa) (molar ratio of L3Ia: L4IIa: Rh = 1.8: 1.8: 1) were used in the catalyst mixture solution. 0.0349 g of compound (11) was added as an organic amine and 1.8283 g of mesitylene was added as a GC standard. After reaching the expected reaction temperature, the reactants were metered thereto.

During the reaction, the pressure was kept constant by adjusting the syngas using a mass flow meter. Samples were taken from the reaction mixture after 12 hours. 42.8 mol% of pentanal, 14.8 mol% of 2-methylbutanal and 2.11 mol% of n-butane were formed. The position selectivity for n-pentanal was 74.4%.

Example 21

In a 100 ml autoclave from Parr Instruments, 6.3 g of cis-2-butene was hydroformylated at 120 &lt; 0 &gt; C and 20 bar. As a precursor, 0.0047 g of Rh (acac) (CO) ₂ was first charged to 43.47 g of toluene. As the ligand, 0.0203 g of the ligand (3Ia) and 0.0576 g of the ligand (4IIa) (molar ratio of L3Ia: L4IIa: Rh = 1.1: 3.1: 1) were used in the catalyst mixture solution. 0.0362 g of compound (11) was added as an organic amine and 1.8681 g of mesitylene was added as a GC standard. After reaching the expected reaction temperature, the reactants were metered thereto. During the reaction, the pressure was kept constant by adjusting the syngas using a mass flow meter. Samples were taken from the reaction mixture after 12 hours. 37.1 mol% of pentanal, 14.3 mol% of 2-methylbutanal and 1.52 mol% of n-butane were formed. The position selectivity for n-pentanal was 72.2%.

Example 22

In a 100 ml autoclave from Parr Instruments, 6.4 g of cis-2-butene was hydroformylated at 120 &lt; 0 &gt; C and 20 bar. As a precursor, 0.0050 g of Rh (acac) (CO) ₂ was _first charged into 43.06 g of toluene. As the ligand, 0.0082 g of ligand (3Ia) and 0.0697 g of ligand (4IIa) (molar ratio of L3Ia: L4IIa: Rh = 0.41: 3.55: 1) were used in the catalyst mixture solution. 0.0374 g of compound (11) was added as an organic amine and 1.7914 g of mesitylene was added as a GC standard. After reaching the expected reaction temperature, the reactants were metered thereto.

During the reaction, the pressure was kept constant by adjusting the syngas using a mass flow meter. Samples were taken from the reaction mixture after 12 hours. 32.7 mol% pentane, 12.5 mol% 2-methylbutanal and 1.12 mol% n-butane were formed. The position selectivity for n-pentanal was 72.4%.

Examples of Expansion Experiments

Example L1: Hydroformylation using ligand (100) not of the invention over 1200 hours (Comparative Example 1)

A ligand of formula (100), which is not of the invention known from EP2280920B1, was used in the hydroformylation of a butene / butane mixture.

(100)

The ligand (100) was stabilized with an amine of formula (11).

&Lt; Formula 11 >

A continuous working experimental system consists of a 20 liter capacity pressure reactor with a downstream condenser, a phase separation vessel (gas / liquid) for the gas phase from the reactor, and a gas phase from the phase separation vessel It was essentially a circulating gas compressor. A portion of this circulating gas has flowed out of the reaction system as exhaust gas after phase separation. In order to achieve an optimum gas distribution in the reactor system, a gas distributor ring having a bore therein was installed. Using the installed heating and cooling apparatus, the temperature of the reactor could be controlled.

Prior to hydroformylation, the system was purged with nitrogen to remove oxygen. Subsequently, the reactor was charged with 12 liters of the catalyst solution.

This catalyst solution contained 12 kg of a eutectic mixture of biphenyl and diphenyl ether (Diphyl®, a heat carrier oil from Lanxess), 3 g of Rh (acac) (CO) 2, 36 g of Bisphosphite ligand of formula 100, 67.5 g of amine of formula 11 and mixed in a vessel in advance. To remove oxygen and water from the heat carrier oil, a eutectic mixture (biphenyl) of biphenyl and diphenyl ether was stripped in advance with nitrogen.

Subsequently, the reactor system was purged with syngas to remove nitrogen. Once the nitrogen content was dropped to less than 10 vol%, the reactor system was pressurized to 1.0 MPa using synthesis gas and then heated to 120 &lt; 0 &gt; C. Upon reaching the operating temperature, the reactor system was brought to a reaction pressure of 1.7 MPa using syngas.

The addition of the starting material was then started. For this purpose, the feed mixture was flowed through an evaporator in order to flow it into the circulating gas in a gaseous form. The feed mixture was a mixture of 35% by weight of 2-butene and 1% of 1-butene. The remainder was n-butane.

The following throughput was fixed: 0.3 kg / h of feed mixture, 75 l (STP) / h of synthesis gas (50% by volume of H2 and 50% by volume of CO).

To daily metered addition of the bisphosphite ligand 100 and amine 11, 1.4 of the bisphosphite ligand 100 in n-pentane (<3%) with residual C4 hydrocarbons removed by stripping with nitrogen in advance % Solution. Amine (11) was used in triplicate to the bisphosphite ligand (100) in molar excess. For better stabilization of this solution, the amine (11) was added to the solution before the bisphosphite ligand (100).

After about 1000 hours, a steady state was reached. The reaction product was continuously removed from the reactor through the circulating gas stream and partially condensed at 50 캜 in a condenser. Subsequently, the condensed phase was flowed out of the phase separation vessel. Samples were taken from the upstream and downstream of the recycle gas in the reactor to determine conversion rates.

By metered addition of the ligand solution described above daily, it was possible to maintain the conversion and position selectivity constant.

To determine the reactor contents, samples were taken from the reactor and analyzed using liquid chromatography (HPLC). Under the selected reaction conditions, about 65-70% of the butene conversion was achieved. The percentage distribution between n-pentanal and 2-methylbutanal, i. e. n / isoselectivity was 95% to 5%. On the steady-state of the experiment, no rhodium decomposition was recorded.

The yield of C5 aldehyde during the experimental period was plotted in Fig.

2: The pentane &lt; RTI ID = 0.0 &gt;

After 1200 hours, the reactor was depressurized and the catalyst solution was analyzed. A precipitate was found in the reactor. Analysis of this precipitate showed that it consisted of bis-phosphite ligand (100) and the phosphorus-containing conversion product of amine (11) used. No caking of these precipitated solids was found in the reactor.

After removal of the precipitate, a portion of the reactor contents was concentrated to 13% based on the starting material at 1.2 kPa (absolute) and bottom temperature 220 [deg.] C. The residue obtained from the liquid was still free flowing and no precipitate was found. The rhodium analysis indicated that all of the rhodium from the starting material was present in these liquid residues.

Example L2: Hydroformylation using ligand 100, which is not of the invention for 8000 hours (Comparative Example 2)

Experiments were performed in the experimental system described in Example L1. Preparation for the experiment and procedure was similar to Example L1.

In this example, the catalyst solution consisted of 12 kg of isononyl benzoate, 4.5 g of Rh (acac) (CO) 2, 55 g of bisphosphite ligand of formula 100, and 67.5 g of amine of formula 11. To remove oxygen and water from the system, isononyl benzoate was similarly pre-stripped with nitrogen.

Subsequently, the reactor system was purged with syngas to remove nitrogen. Once the nitrogen content was dropped to less than 10 vol%, the reactor system was pressurized to 1.0 MPa using synthesis gas and then heated to 120 占 폚. Upon reaching the working temperature, the reactor system was brought to a reaction pressure of 1.7 Mpa using syngas.

Subsequently, the addition of the starting material was started. For this purpose, it was flowed through an evaporator to allow the feed mixture to flow in a gaseous form into the circulating gas. The feed mixture was a mixture of 35% by weight of 2-butene and 1% of 1-butene. The remainder was n-butane. The following throughput was fixed: 0.3 kg / h of feed mixture, 75 l (STP) / h of synthesis gas (50% by volume of H2 and 50% by volume of CO).

(1.4) of the bisphosphite ligand (100) in n-pentane in which residual C4 hydrocarbons have been removed (< 3%) in advance by stripping with nitrogen to add the bisphosphite ligand 100 and amine % Solution. Amine (11) was used in triplicate to the bisphosphite ligand (100) in molar excess. For better stabilization of this solution, the amine (11) was added to the solution before the bisphosphite ligand (100).

As in Example L1, a steady state was reached after about 1000 hours. The reaction product was continuously removed from the reactor through the circulating gas stream and partially condensed at 50 캜 in a condenser. Subsequently, the condensed phase was flowed out of the phase separation vessel. Samples were taken from the upstream and downstream of the recycle gas in the reactor to determine conversion rates.

By metered addition of the ligand solution described above daily, it was possible to maintain the conversion and position selectivity constant.

To determine the reactor contents, samples were taken from the reactor and analyzed using liquid chromatography (HPLC). Under the selected reaction conditions, approximately 65-70% of the butene conversion was achieved. The percentage distribution between n-pentanal and 2-methylbutanal, i. e. n / isoselectivity was 95% to 5%. On the steady-state of the experiment, no rhodium decomposition was recorded.

The yield of C5 aldehyde during the experimental period was plotted in Fig.

3: The pentane &lt; RTI ID = 0.0 &gt;

After 1500 hours, a first precipitate was found in the sample from the reactor. As in Example L1, analysis of these precipitates showed that they consisted of bis-phosphite ligand (100) and the phosphorus-containing conversion product of amine (11) used.

The reaction was carried out for a total of 8100 hours; The rhodium loss through sampling was supplemented by the addition of a corresponding amount of Rh (acac) (CO) 2 to the ligand metering solution daily.

After about 7000 hours, as the reaction progressed, a decrease in activity was found in the reaction, and the reaction solution tended to foam. It was no longer possible to run the process and the experiment had to end.

After completion of the reaction, the reactor was depressurized and the reaction mixture was analyzed. A large amount of solid was found. 250 ml of the reaction solution was stirred at 40 &lt; 0 &gt; C for 4 hours under N2 atoms, and then the viscosity of the residue was measured. The viscosity was 300 mPas.

Example L3: Hydroformylation using the catalyst system of the present invention

The same experimental system as in Example L3 was used. The same feed mixture and the same synthesis gas were used. However, the ligand used was a mixture of two bisphosphite ligands (Ila) and (IIla). The ligand of formula (100) known from EP2280920B1 was not present in the reaction mixture. The same amine (11) as in Comparative Example 1 (L1) was used as the stabilizer. The solvent used was isononyl benzoate.

Prior to hydroformylation, the system was purged with nitrogen to remove oxygen. Subsequently, the reactor was charged with 12 liters of the catalyst solution.

This catalyst solution consisted of 12 kg of isononyl benzoate, 4.5 g of Rh (acac) (CO) 2, 63 g of the ligand isomer mixture of formulas Ila and 2IIa, 200 g of amine of formula 11, Lt; / RTI &gt; To remove oxygen and water from the solvent, isononyl benzoate was pre-stripped with nitrogen.

Subsequently, the reactor system was purged with syngas to remove nitrogen. Once the nitrogen content was dropped to less than 10 vol%, the reactor system was pressurized to 1.0 MPa using synthesis gas and then heated to 120 &lt; 0 &gt; C. Upon reaching the working temperature, the reactor system was brought to a reaction pressure of 1.7 MPa using syngas.

The addition of the starting material was then started. The feed mixture was flowed through an evaporator in order to flow the gas into the circulating gas in a gaseous form. The following throughputs were fixed: 0.3 kg / h of feed mixture, 75 l (STP) / h of synthesis gas.

(&Lt; 3%) of residual C4 hydrocarbons by stripping with nitrogen to make daily metering of the isomeric mixture of (1Ia) and (IIIA) and amine (11) A 1.4% solution of the ligand mixture of (1Ia) and (2IIa) was constructed. Amine (11) was used in triple molar excess with respect to the ligand isomer mixture of (1Ia) and (2IIa). For better stabilization of this solution, the amine (11) was added to the solution before the bisphosphite ligand isomer mixture.

The reaction product was continuously removed from the reactor through the circulating gas stream and partially condensed at 50 캜 in a condenser. Subsequently, the condensed phase was flowed out of the phase separation vessel. To determine the yield, samples were taken from upstream and downstream of the recycle gas in the reactor and analyzed using a gas chromatograph.

By metered addition of the ligand solution described above daily, it was possible to maintain the conversion and position selectivity constant. To determine the reactor contents, samples were taken from the reactor and analyzed using liquid chromatography (HPLC).

Under the selected reaction conditions, aldehyde yields between 80% and 90% were reached at the beginning of the reaction. After 8000 hours of operation, the yield dropped to about 65% due to the rhodium loss from the sampling. In this case, there was no foaming of the detectable reaction solution. The percentage distribution between n-pentanal and 2-methylbutanal, i.e., the position selectivity, was 92% to 8%.

Aldehyde yield and position selectivity during the experimental period are plotted in FIG.

4: Aldehyde yield and position selectivity for Example L3

On the steady-state of the experiment, in addition to rhodium loss due to sampling, no additional rhodium decomposition was recorded.

The rhodium concentration in the reactor during the experimental period was plotted in Fig.

5: The Rh concentration for Example L3

After completion of the reaction, the reactor was depressurized and the reaction mixture was analyzed. No solids were found. 250 ml of the reaction solution was stirred at 40 DEG C for 4 hours under N2 atmosphere, and then the viscosity of the residue was measured. The viscosity was 20 mPas.

Comparison of Examples L1, L2 and L3

In comparison of the examples, Example L3 performed in accordance with the present invention was clearly distinguished from Examples L1 and L2, which show prior art by the following features:

Example L3 of the present invention did not show any internal-flow phase, indicating that the system did not exhibit any activity reduction at the first operating time of 1000 hours and thus the plant in Example L3 of the present invention was very It means that more products are produced.

In Comparative Example 2 (L2), solids that could only be removed by uncomfortable filtration were generated during the reaction. In Example L3 of the present invention, no generation of solids occurred even after 8000 hours, so it was possible to eliminate filtration in this process.

In Comparative Example 2 (L2), at the end of the experiment, significant foaming of the reaction solution occurred and the process could no longer run. This behavior could only be prevented by an uncomfortable foam breaker. The process according to the invention did not require such adjuvants.

Claims (19)

A mixture comprising the following compounds (Ia) and (IIa):
<Formula Ia>

<Formula IIa>

In this formula,
R1 is selected from -Me, -tBu, -OMe;
R2 is selected from -Me, -tBu, -OMe;
R3 is selected from -Me, -tBu, -OMe;
R4 is selected from -Me, -tBu, -OMe;
only,
When R1 is the same as R3, R2 is not the same as R4,
When R2 is the same as R4, R1 is not the same as R3,
P can participate in an additional combination. The mixture according to claim 1, wherein the content of the compound (Ia) is in the range of 99.5 to 0.5 mass% and the content of the compound (IIa) is in the range of 0.5 to 99.5 mass%. 3. A mixture according to claim 1 or 2, comprising the following compounds (Ib) and (IIb).
(Ib)

<Formula IIb>

Wherein M is selected from Fe, Ru, Os, Co, Rh, Ir, Ni, Pd,
M can participate in additional joins. The mixture according to any one of claims 1 to 3, which comprises the following compounds (Ic) and (IIc).
<Formula I>

<Formula IIc>

In the above formula, M is selected from Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and Pt. The mixture according to claim 4, further comprising at least one compound (Ia) or (IIa) which is not bound to M. The mixture according to claim 4 or 5, wherein M is Rh. 7. The mixture according to any one of claims 1 to 6, wherein R1 is -Me and R3 is not -Me. 8. The mixture according to any one of claims 1 to 7, wherein R2 is -Me and R4 is not -Me. 9. The mixture according to any one of claims 1 to 8, wherein R1 and R2 are each -Me. 7. The mixture according to any one of claims 1 to 6, wherein R1 is-tBu and R3 is not-tBu. 7. The compound according to any one of claims 1 to 6, wherein R2 is -OMe and R4 is not -OMe. A mixture according to any one of claims 1 to 11, and
- additional components selected from bases, organic amines, epoxides, buffer solutions, ion exchangers
&Lt; / RTI &gt; 13. The composition of claim 12, wherein the organic amine has at least one 2,2,6,6-tetramethylpiperidine unit. a) oxidative coupling according to Scheme A,
<Reaction Scheme A>

b) oxidative coupling according to Scheme B below,
<Reaction Scheme B>

c) a step of reacting the product from a) with PCl ₃ according to Scheme C below, and
<Reaction formula C>

d) reacting the product from b) with the product from c) to give the mixture according to claim 1,
Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt; 15. The method of claim 14,
e) reacting with M to produce (Ib) and (IIb), wherein M is selected from Fe, Ru, Os, Co, Rh, Ir, Ni, Pd,
&Lt; / RTI &gt; A composition according to claim 12 or 13, and
- a gas mixture containing carbon monoxide and hydrogen
, &Lt; / RTI &gt; and mixtures thereof. 17. The process of claim 16, wherein the unsaturated compound
A hydrocarbon mixture from a steam cracking plant;
A hydrocarbon mixture from a catalytic cracking plant;
A hydrocarbon mixture from an oligomerization operation;
A hydrocarbon mixture comprising a polyunsaturated compound;
- unsaturated carboxylic acid derivatives
&Lt; / RTI &gt; 18. The method of claim 17, wherein the hydrocarbon mixture comprises an unsaturated compound having from 2 to 30 carbon atoms. 12. The use of a mixture according to any one of claims 1 to 11 as a catalyst in the hydroformylation reaction of unsaturated compounds and mixtures thereof.

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